Polymer 46 (2005) 1263712640

www.elsevier.com/locate/polymer

Critical length of straight jet in electrospinning

Ji-Huan He a,*, Yue Wu b, Wei-Wei Zuo c
a

College of Science, Donghua University, P.O. Box 471, 1882 Yanan Xilu Road, Shanghai 200051, China
b
College of Textile Science, Donghua University, Shanghai, China
c
College of Material Science and Engineering, Donghua University, Shanghai 200051, China
Received 6 August 2005; received in revised form 22 October 2005; accepted 27 October 2005
Available online 14 November 2005

Abstract
In this paper the well-known Chauchys inequality is applied to prediction of critical length of the straight jet in electrospinning. A critical
relationship between radius r of jet and the axial distance z from nozzle is obtained for the straight jet. Critical length number and critical radius
number are defined, which might be found potential applications in experiment and apparatus design.
q 2006 Published by Elsevier Ltd.
Keywords: Electrospinning; Critical length number; Critical radius number

1. Introduction
Electrospinning [16,814,1729,32] is a process, which
produces superfine fibers. The produced nanofibers of polymer
can find wide applications in various areas, such as air
filtration, water filtration, agricultural nanotechnology, wound
dressing, bone tissue engineering, drug delivery, just say few.
The procedure involves applying a very high voltage to a
capillary and pumping a polymer solution through it.
Nanofibers of polymer collect as a nonwoven fabric on a
grounded plate below the capillary.
Electrospinning has been caught much attention recently,
much work on experimental investigation, mathematical
modeling, and instability analysis is appeared in open
literature.
Deitzel et al. [2] studied systematically the effects of two of
the most important processing parameters: spinning voltage
and solution concentration, on the morphology of the fibers
formed; Theron et al. [24] studied the influence of different
process parameters on the electric current and volume and
surface charge density in the polymer jet; Theron et al. [25]
also investigated and modeled multiple jets during the
electrospinning of polymer solutions.
Fridrikh et al. [3] suggested a simple analytical model for
the forces that determine jet diameter during electrospinning as
* Corresponding author. Tel.: C86 21 623 79917; fax: C86 21 623 73926.
E-mail address: jhhe@dhu.edu.cn (J.-H. He).

0032-3861/$ - see front matter q 2006 Published by Elsevier Ltd.

doi:10.1016/j.polymer.2005.10.130

a function of surface tension, flow rate, and electric current in

the jet; Canan-Calvo [4,5] suggested some asymptotic scaling
laws in electrospraying. Many other valuable mathematical
models exit in open literature, and the analytical relationship
between radius r of jet and the axial distance z from nozzle has
been the subject of regular investigation since the electrospinning process was first patented by Formhals in 1934. Spivak et
al. obtained the following relation [22]:


K2 m 
d
K4
K1
K1 2
K1 dR
R C Nw R KNE R KNR
Z1
(1)
dZ
dZ
where R is the dimensionless jet radius, Z is the dimensionless
axial coordinate, Nw, NE and NR are, respectively, the Weber
number, Euler number, and the effective Reynolds number.
Spivak et al. [23] obtained a power-law asymptote with an
exponent K1/4 for the jet radius:
R wZK1=4

(2)

Shin et al. [21] reported an experimental investigation of the

electrically forced jet, and the data reveals that the radius
decreases as z increases. Rutledges group suggest the
following relationship [20]
p
6mrQ2 1
(3)
rZ
z
pIE
The regulation of scale in electrospinning is an intriguing
and enduring problem. Ji-Huan Hes group also obtained some
scaling relationships between the radius of the electrically
driven jet and the distance from the orifice [9]: rwzK1/2 for the
initial steady stage, rwzK1/4 for instability stage, and rwz0

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J.-H. He et al. / Polymer 46 (2005) 1263712640

terminal stage by allometrical method, which is widely applied

in biology [7,12,15,16] and in polymer [9,11,13,14] as well.
The instability in the electrospinning procedure has been
widely studied recently. Hohman et al. [6] analyzed the
mechanics of the whipping jet by studying the instability of an
electrically forced fluid jet with increasing field strength; Qin et
al. [17,18] used Polyacrylonitrile (PAN) to study experimentally the effect of the instability on electrospinning nanofibers
by adding LiCl; Reneker et al. [19] analyzed the reasons for the
instability and explained the phenomenon using a philosophic
mathematical model; Shin et al. [21] reported an experimental
investigation of the electrically forced jet and its instabilities;
Yarin et al. [28] suggested a localized approximation to
calculate the bending electric force acting on an electrified
polymer jet, which is a key element of the electrospinning
process for manufacturing of nanofibers. Using this force, a far
reaching analogy between the electrically driven bending
instability and the aerodynamically driven instability was
established; Zuo et al. [32] predicted three types of instabilities
for an electrically driven jet: the axisymmetric Rayleigh
instability, the electric field-induced axisymmetric, and
whipping instability.
Our group also suggested a revised formulation for the
calculation of resistance for non-conductors [11,12,14], and
applied the vibration technology to electrospinning [10]. The
purpose of application of vibration to polymer solution is to
reduce its viscosity [30,31].
In this paper, we will use the well-known Chauchys
inequality
1
ab% a C b2 ;
4

aO 0; bO 0

(4)

to predict the critical length of the straight jet of the

electrospinning from a capillary orifice to the point where
instability occurs, i.e. the length of AB in Fig. 1.
2. Critical length number for electrospinning
After decades of concentrated effort, much progress has
been made. This paper will provide a rational theory, which can
predict simply the length of the straight jet in the electrospinning. For sake of clarity and avoiding unnecessary complexity,

we consider a steady state flow of an infinite viscous jet pulled

from a capillary orifice and accelerated by a constant external
electric field.
Conservation of mass gives
pr 2 ru Z Q

(5)

where Q is the flow rate, r is radius of the jet, u is the velocity.

Letting the surface charge be s, conservation of charges
gives [4,5]
2prsu C kpr 2 E Z I

(6)

where k is the dimensionless conductivity of the fluid, E

applied electric field, and I is the current passing through the
jet.
Force balance gives [8]

2
d u
2sE 1 dt
C
(7)
Z
dz 2
rr
r dz
where r is the liquid density, the last term of the right side of
Eq. (7) is viscous force, where t can be expressed in the form.

2nC1
m
du X
du
t ZKp C m0 C
an
(8)
dz nZ1
dz
where p is the internal pressure of the fluid expressed as
p Z kgK

3K3 2
E K2p3s2
8p

(9)

where k is twice the mean curvature of the interface kZ1/R1C

1/R2, here R1 and R2 are the principal radii of curvature, 3 is the
fluid dielectric constant, 3 air dielectric constant.
Please note that other more useful rheological models are
suggested by some authors. Theron et al. [24,25] Yarin et al.
[27], Reneker et al. [19] suggested some more realistic
viscoelastic models for electrospinning.
Using the Chauchys inequality (4), and in view of Eq. (6),
from Eq. (7) we obtain the following inequality


d u2
2prsu !kpr 2 E 1 dt
C
Z
dz 2
r dz
p2 rkr 4 u
%

2prsu C kpr 2 E2 1 dt
C
r dz
4p2 rkr 4 u

I2
1 dt
C
4pkQr 2 r dz

(10)

The critical value occurs when

2prsu Z kpr 2 E

(11)
2

In view of Eq. (5), we have uZ Q=pr r. Substituting it to

(11), we obtain



2sQ 1=3
(12)
rZ
pkrE
Fig. 1. Critical straight length (AB) in electrospinning.

In this paper we limit ourselves to the initial stage of the

electrospinning. In order to avoid misunderstanding, we give a

J.-H. He et al. / Polymer 46 (2005) 1263712640

12639

clear illustration of the electrospinning process. In case when

electrical force is zero or weakly, a pendant droplet of the
polymer solution at the capillary tip is deformed into a conical
shape (Taylor cone), where the surface tension is dominant. If
the voltage surpasses a threshold value, electrostatic force
overcomes the surface tension and viscous force of the jet, and
a fine charged jet is ejected. In this initial stage, electrical force
is dominant, or the jet cannot be ejected. Due to the electrical
force, the jet is accelerated. During the acceleration, however,
the viscous resistance prevents the jet from moving forward, as
a result the acceleration becomes smaller and smaller. When
the acceleration become zero or a constant, any small
perturbation will destroy its straight movement, and instability
occurs (the point B in Fig. 1), detailed geometrical analysis of
the instability was illustrated in Ref. [9]. When z/N (i.e.
close to the jet breakup), surface charge advection is dominant.
We limit ourselves to the initial stage, i.e. AB in Fig. 1. In this
stage, electrical force is dominant over other forces acting on the
jet, so the inequality (10), by simply operation, reduces to
d K4
pr2 I 2 K2
r %
r
dz
2kQ3

(13)
Fig. 2. Experiment set-up.

from which we can immediately obtain

rK2 %

pr2 I 2
2
z C rK
0
4kQ3

(14)
Table 1
d0 and z0 are diameter and coordinate respectively at the point where instability
occurs

which can be re-written in the form

1
rR p
2
bz C rK
0

(15)

where b is defined as minimal radius number defined as

bZ

pr2 I 2
4kQ3

(16)

Voltage
Current
Flow rate
d0
z0

PHBV

Cellulose

30 kV
500 nA
2 ml/h
80 mm
6 cm

30 kV
35 nA
2 ml/h
105 mm
2 mm

We modify (15) in the following form in order to describe the

actual electrospinning
r0
r Z armin Z a p
(17)
br02 z C 1
which corresponds to rwzK1/2 obtained in Ref. [9] for initial
stage. Hereby a is an unknown function of the viscosity of
polymer solution, aZa(m), which can be determined experimentally or theoretically.
The minimal value of r in the initial stage reads
r0
rmin Z Rcr Z p
br02 L C 1

(18)

where L is the length of the straight length (AB in Fig. 1) of the

electrospun fiber, and we call Rcr critical radius number.
In view of (12), we have the relationship
s



2sQ 1=3
4kQ3 r02
Z
(19)
2
2
pkrE
pr I r02 L C 4kQ3
from which we can obtain the critical straight length (AB in
Fig. 1) from the capillary orifice to the point where instability

Fig. 3. The dimensionless jet diameter d/d0 vs the dimensionless axial

coordinate z/z0. d0Zd(0), and zZz0 is instability point (i.e. the point B in Fig. 1).

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J.-H. He et al. / Polymer 46 (2005) 1263712640

occurs




1
pkrE 2=3 K2
Kr0
b
2sQ





4kQ3
pkrE 2=3 K2
4kQ3 2 K2

Z 2 2
Kr0 Z 2 2 RK
0 Kr0
2sQ
pr I
pr I

L Z zcr Z

(20)

where R0 Z 2sQ=pkrE1=3
We call L the critical length number.
In order to verify our prediction, we have made an
experimental verification. The apparatus used in the work is
designed to ensure operation in a uniform voltage and flow rate.
Fig. 2 is the experiment set-up, we use poly(hydroxybutyrateco-valerate) (PHBV) and cellulose as solutions. Table. 1
illustrates parameters applied in the experiment. Fig. 3 shows
that our prediction rwzK0.5 at initial stage is in well agreement
with the experimental observations, rwzK0.44 for poly(hydroxybutyrate-co-valerate) and rwzK0.54 for cellulose.
3. Conclusion
The preceding analysis is of course rather crude but has the
virtue of utter simplicity and importance. Our inequality
approach to critical length of the straight jet in electrospinning
is of a general philosophical framework for determination of
the instability point of the jet, and it is much more effect and
convenient than any other conventional approaches such as
numerical method, analytical method, and experiment method.
In this paper, critical length number, and critical radius number
are first introduced, which, like well-known Reynolds number
in fluid mechanics, might be some applications in experimental
and apparatus design.
Acknowledgements
The work is supported by grant 10372021 from National
Natural Science Foundation of China and the Program for New
Century Excellent Talents in University. The experiment
verification is done by Wei-Wei Zuo.
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